Bf3-iodine polymerization of unsaturated hydrocarbon mixtures



Patented Mar. 17, 1953 BFa-IODINE POLYMERIZATION OF UNSATU- RATED HYDROCARBON MIXTURES Francis T. Wadsworth, Dickinson, Tex., assignor to Pan American Refining Corporation, Texas City, Tex., a corporation of Delaware No Drawing Application December 20, 1951, Serial No. 262,671

Claims. (01. 260-82) This invention relates to synthetic resins and particularly to synthetic hydrocarbon resins. More specifically, my invention relates to the production of synthetic hydrocarbon resins of improved color from a mixture of unsaturated hydrocarbons obtained in the high-temperature pyrolysis of normally gaseous hydrocarbons.

Many methods are disclosed in the prior art for preparing resins from unsaturated hydrocarbons by catalytic and non-catalytic polymerization thereof. Qne suitable type of unsaturated hydrocarbon mixture can be produced by the high-temperature pyrolysis of normally gaseous hydrocarbons, in which treatment the hydrocarbons undergo a complex group of reactions, including cracking, dehydrogenation, conjugation, aromatization, polymerization, and the like, whereby the hydrocarbons are converted into-a heterogeneous mixture comprising olefins, diolefins, cycloolefins, aromatics, and a variety of other derivatives of diverse physical properties, the entire mixture extending in complexity from ethylene to solids of high melting point. This mixture can be separated or converted into a number of useful products, including pure aromatics, pure olefins, diolefins, and resins. The resins have in general been of limited utility, however, owing to their comparatively dark color, their color instability, and their tendency toward mechanical failure during aging. Moreover, the resins have exhiibted little or no response to the usual methods of decolorizing, such as treatment with strong mineral acids or with adsorbent solids.

I have now discovered a method whereby stable resins of light color and low iodine number can be prepared from certain unsaturated hydrocarbon mixtures and fractions thereof, obtained ashereinafter described by pyrolysis of normally gaseous hydrocarbons containing two or more carbon atoms in the molecule. My improved resins are obtained by polymerizing an unsaturated hydrocarbon charging stock of the aforesaid class at a temperature above about 500 F. in the presence of catalytic proportions of boron trifluoride and iodine.

One object of my invention is to prepare a hydrocarbon resin of improved chemical and physical properties. Another object is to prepare a hydrocarbon resin of low iodine number, light color, and improved stability. A further object is to prepare a useful hydrocarbon resin from an unsaturated liquid mixture obtained in the pyrolysis of normally gaseous hydrocarbons. A still further object is to reduce the effect of oxidizing agents and organic oxygenated compounds during the BFg-polymerization of unsaturated hydrocarbon mixtures. Other objects of my invention and its advantages over the prior art will he -apparent from the present description thereof and from the appended claims.

The charging stock in my process is an unsaturated hydrocarbon liquid or fraction thereof commonly referred to as Dripolene, which is obtained as a by-product from the high-temperature pyrolysis of a normally gaseous hydrocarbon containing two or more carbon atoms in the molecule, or a mixture of such hydrocarbons such as natural gas or by-product gases from the cracking of heavy petroleum oils in the manufacture of gasoline. In the preparation of Dripolene, a gaseous hydrocarbon or mixture ..of hydrocarbons, preferably propane, a mixture of propane and propylene, or a natural gas rich in propanes and/ or butanes is preheated and passed through an alloy tube in a furnace, whereit is exposed at high space velocity tov a pyrolysis temperature of at least about 1300 F., preferably between about 1350 and 1550 F. Low or moderately elevated pressures up to about pounds per square inch are ordinarily employed in this operation, a pressure of 5 to 40 pounds per square inch gage at the reactor outlet being generally used. The stream of gas should be passed through the furnace at high velocity, so that the time of exposure to the high temperature is limited to about 0.2 to 5 seconds, around 1 second being preferred.

The hot gases leaving the pyrolysis zone are immediately cooled below reaction temperature, preferably below about 100 F., by quenching with a stream of water, oil, or other cooling medium, whereby further pyrolysis, polymerization, or degradation of the reaction product is prevented. From a quenching zone, a liquid-phase mixture of the cooling medium and unsaturated hydrocarbons is withdrawn, the latter being known in ,the art as Dripolene." The Dripolene is separated from the quenching liquid by stratif cation (where the two liquids are immiscible, as from water), or by distillation (as from an absorber oil). The yield of liquid hydrocarbons is ordinarily around 3 percent by weight of the total quantity of gas charged to the pyrolysis zone, the remainder of the gas being converted to lower-molecular-weight hydrocarbons such as ethylene and methane, and to hydrogen. A typical specimen of Dripolene has the following properties and composition:

3 ASTM distillation range, F.:

Initial 100 10% 146 20% 162 30% 1'78 40% 188 50% 196 60% 206 70% 234 80% 296 90% 340 Final 360 Gravity, API at 60 F 34.7 Bromine number, cg. Br2/g 104.1 Maleic anhydride value, mg. M. A./g 79 Index of refraction, n 1.4830

Analysis, volume-percent:

Propane and propylene Isobutane Q Isobutylene l-butene Z-butene n-Butane Butadiene Pentadienes Pentylenes Other C5 0.4 Benzene 34.2 Toluene 7.8 Xylenes 1 Styrene 3 a I Dicyclopentadiene 5 Other 29.6

' Fonthe charging stock in the preparation of resins by my new process I can employ the total Dripolene mixture obtained as described above, or a distillate or bottoms fraction thereof. An especially desirable charging stock is a 70 to 90 percent Dripolene distillate fraction, such as a so-called80 percent Dripolene overhead fraction, obtained by fractionally distilling the total Dripolene and separating therefrom the desired proportion of the Dripolene as a distillate fraction. Other fractions can also be employed satisfactorily in the process of my invention, yielding resins of somewhat difierent characteristics.

Inpracticing my invention, a Dripolene charging stock is combined with iodine and boron trifluoride, and the mixture is heated topolymeriza tion temperature. Thereafter, the reaction prod uct is depressurized and stripped of BF3, and is finally subjected to any-additional desired purification treatment. The iodine should be used in a minimum proportion of about 0.02 percent by weight, preferably between about 0.02 and 2, optimally around 0.05. The BFa should be used in a proportion between about 0.5 and 5 percent by weight, optimally around 3. The reaction temperature should be between about 500 and 650 F., optimally about 575 F., and should be maintained for about 0.1 to hours, preferably 0.25 to 1 hour. Removal of the BF: is preferably effected by flashing or stripping at a temperature withinjthe polymerization range:

In'one" embodiment, my new process comprises the following steps: A Dripolene charging stock is introduced into an evacuated or gas-blanketed pressure-type reactor. Crystalline iodine (around 0.05 percent by weight) is commingled therewith, and BF3 (around 3 percent) is slowly introduced into the reaction zone while the reaction mixture is agitated by suitable means. The BF; addition rate is preferably regulated so that the temperature does not exceed 120.F. during the catalyst addition. After all of the BFa has been added, the mixture is heated rapidly with agitation to a temperature of about 575 F., where it is maintained for about 30 minutes. At the end of this time, the BF: is flashed oiT at a temperature between about 500 and 650 F. The resulting resin ordinarily has a Barrett color of about 4 or lighter, and can be further decolorized if desired by methods known in the art. Thereafter, it is stripped with a gaseous hydrocarbon or other inert gas to a ring-and-ball softening point of about 150 to 250 F. A purified resin is obtained thereby, having a Barrett color lighter than 4, an iodine number less than about (ordinarily between about 30 and 50), and excellent resistance to deterioration in color and mechanical structure with age.

The supplemental decolorization, referred to above, can be efiected by agitating the resin at ordinary temperatures with about 5 to 15 pounds per barrel of percent sulfuric acid. Substantially any other strong mineral acid, such as phosphoric acid, hydrogen fluoride, and the like, can also be used for this purpose. Any suspended acid can be removed from the resin by washing with caustic or ammonium hydroxide, by filtration through soda lime, or by filtration through clay or other adsorbent solid. Suitable adsorbent solids include bauxite, silica gel, magnesium silicate, kieselguhr, infusorial earth, diatomaceous earth, and various clays, such as fullers'earth and bentonite, whichcontain predominantly aluminum silicates. Among the more commonly used clays are Attapulgus' clay and the Florida earths, generally known by trade names such;as Floridin and Florex. Clay filtration after acid treatment is not only an effective method of removing the suspended acid, with an excellent clay life of over 50 barrels of resin per ton of clay, but it also produces an additional degree of decolorization. Clay filtering alone, without prior acid treatment, is also an eifective method for color improvement.

An essential feature of my invention lies in the simultaneous exposure of my charging stock to the action, of iodine and BFz. A preliminary treatment ,of the charging stock with iodine alone, followed by polymerization in the presence of BF3 alone, is inefiective to produce resins of light color; it appears, therefore, that the action of iodine and BFs is synergistic in nature.

An important feature of my invention is the polymerization temperature, which should lie between about 500 and 650 F., preferably around 575 F., varying inversely as a function of the BFs concentration. For example, at a BF'zconcentration of 5 percent by weight, the optimum polymerization temperature lies between about 500 and 525 F., and at a BF: concentration of 0.5 percent by weight, the optimum lies between about 625 and 650 F. The optimum temperature does not appear to vary substantially with the iodine concentration. Under the foregoing conditions, resins are produced which are substantially Iighterincolor than resins produced under other conditions.

Another important feature of my invention is the step of. hot-flashing the BF3 from the polymerized charging stock at a temperature within the polymerization range. If the polymerization mixture is cooled before removal of the BF3, it is generally necessary to reheat the mixture in order to expel the BF's, and the quality of the resin is thereby impaired.

' Water and oxygenated organic compounds have a detrimental influence .in my process, and should therefore be removed and/or excluded substantially completelyfrom the charging stock and other process materials. 'This can be effected by passing the materials through a bed of calcium chloride, anhydrous sodium sulfate, soda lime, or other dehydrating solid which has no appreciable polymerizing effectupon the unsaturated components thereof. Surface-active adsorptive solids such as silica gel and aluminum oxide are unsuitable, since they appear to cata lyze exothermic reactions in the charging stock, and lead to the production of undesirably dark resins.

For the same reason, complexes of borontrifluoride with organic oxygenated compounds are not suitable as catalysts in my process, although they have been widely used as catalysts in other polymerization processes. My process employs boron trifluoride alone, in combination with iodine, but it will be understood that the catalyst can be permitted to include ingredients which are inert under the reaction conditions. The iodine is preferably introduced .into the reaction mixture in .the crystalline form or as ,a solution in a suitable inert solvent. :The BB; is

preferably introduced as a gasiform stream into the polymerization zone with vigorous agitation in order to minimize the occurrence of local Example I The effect of iodine concentration was studied in a series of polymerization tests on a number of 80 percent overhead Dripolene distillate fractions. The Dripolene stock was introduced into a high-pressure reaction bomb with the desired proportion of BFs and iodine. The bomb was he te o 0 25 mi ut s t a ga b ne to a maximum temperature of 550. Fi land the temperature was maintained at 550 F. for an additional 15-minute period. The reaction product thereafter flashed and stripped at .reaction temperature .to ,a ,ball and-ring softening pointiof zoo-$219315. Theresults .wereas i 'o1lows:

BF t 1 t Ream R 13 1 o d B aw 2, w V eae or: le ar ner arrett DIXDPIBHB Stock 'p'eroent percent 3 3?" Time, wt."per- Color Color 1 m n cent 3. 0 0. 020 550 .33. 5 l4. 5 3. 5 3. 0 0. 020 550 35 E34. 5 15 4 3.0 0.012 550 35 36.0 16 4 3.0 0.020 550 13,5 36.6, 14.5 3. 5 3.0 O. 010 550 .35 33 .16 4" 3.10 0. 020 5 50 55 132.6 14.5 3.5 3.10 0. 020 5 50 35 33.5 14. 5 3:;5

transient zones of .high catalyst concentration therein.

The polymerization can optionally be carried out in an inert solvent for the final resin, such as a light petroleum naphtha, benzene, toluene, xylene, isooctane, gasolineor other aromatic or aliphatic hydrocarbon liquid or mixture thereof. The presence of such a solvent is especially desirable during any supplemental decolorization step or steps, since the polymerization product is ordinarily so viscous that it cannot be satisfactorily contacted in undiluted form with a decolorizing agent. The solvent is conveniently employed in a ratio between about 0.25 and 5 volumes per volume of charging stock. The greater part of the solvent can readily be removed from the polymerization product by distillation, the residual portion being removed in the final stripping of the resin.

The products of my invention are resins of iodine number below about 80, ordinarily between about-30 and "50, of color lighter than about The .fQ iegoing data show that aniodine concentration ofthe order of 0.020 weight-percentis effective in improving the color of Dripolene resins from 16 Gardner (dark red) to around 14.5 Gardner (between pale and light red).

Example II The effect of iodine concentration was further studied in the following series of experiments. In each experiment, an 80 percent overhead Dripolene distillate fraction was charged with BF:; and iodine into a high-pressure reaction bomb'fandthebomb Was heated for 30 minutes to a maximum temperature of 575 F. and main- Total Resin 1 D I n Sm k QBF wt. ImWt. $3355 9 Reaction Yield, Gardner Barrett p? c percent 1 percent L, F Time, wt. perolor Color 1 nun. cent p emiere foregoing data it appears-inserts color improvement is attained at an iodine concentration" "of approximately 0.03 weight-percent. I v Example III In order to ascertain the optimum temperature for polymerizing Dripolene with BF: and iodine,

In order to evaluate the importance oi agitation during polymerization of an 80 percent overhead Dripolene distillate fraction with BF: and iodine, a number 'of experiments were carried out in which the reaction bomb was heated electrically to 575 F. without shaking. A period of 2.5 hours was required to reach this temperature, at which point the bomb was depressured and 10 the contents were stripped to a 200-210 F. softening point. The following results were obtained:

a series of tests were carried out on an 80 percent overhead Dripolene distillate fraction in which the" BF's and iodine concentrations were main-' tained substantially constant while the polymeri= Resin Dripolene BF3,wt. 'I2,wt. Bffgg fggg Yield, I NO Gardner Barrett Stock percent percent F min wt. pter- 2 Color Color w cen These data demonstrate that light-colored resins are produced by carrying out the polymerization Without agitation. From this it follows that the reaction system is homogeneous under the reaction conditions, and that agitation is of benefit only in reaction equipment having poor heattransfer characteristics. 7

'z'atio'ntemperature was chosen within the range of '550 to 650 F. The'c'omplet reaction mixture was raised to the desired reaction temperature 5 over aperiodof 30 minutes, and was then held atthe reaction temperature for an additional peac of 15 to "minutes as indicated below. The procedure employed was otherwise substantially the same as in Example I. The following 7 Example VI results were obtained: A group of polymerization tests were carried Total Resin Reaction M BF wt. I wt. Reaction Y1eld,- Gardner Barrett Dnpolene stock per cent prcent T???" Time, wt. per- Color Color 7 min. cent 3.4 0.02 550 31.2 17 4.5 3. 2 0. 02 580 45 29. 4 15. 5 4 s. s 0.02 600 28.9 16 4. a s. 1 0.02 650 as 26. 4 1s 5 out on miscellaneous charging stocks at 575 F.

These results indicate that both the color and according to the procedure employed in Example the yield of resins are best at temperatures around 580 F. v 1 II. The results were as follows:

' Total Resin Reaction BFQ, wt.. I2, wt. Reaction Yield, Gardner Barrett Dripolene Stock percent percent 2 Time, wt. per- Color Color min. cent E 3. 3 0. O2 575 45 28. 4 l6 4 F--. 3.2 0.03 575 45 27.0 14 3 F 3. 4 O. 03. 575 .45 30. 4 l4. 5 3. 5

G 3. 0 O. 03 575 45 30. 6 14 3 H 3. 2 0. 03 575 45 29. O 14. 5 3. 5

J' 3. 2 O. 03 575 45 29. 0 l4 3 J'- 3. 3 0. 03 575 45 28 O 14. 5 3. 5

Example VII The .following experiments were carried out to compare BFs-iodine polymerization with a two-step process employing an iodine pretreatment followed by polymerization with BF: alone.

Example IV percent. The following data were obtained: An percent overhead Dripolene distillate Total Resin Reaction -BF3' wt. 1:, wt. 1 Reaction Yield, Gardner Barrett Dnpolene stock percent .percen 9 Time, wtuper- Color 7 ;Color Y min; cent fraction was charged with 0.03 weight-percent iodine into a reaction bomb. The mixture was heated for minutes to a maximum tempera- Under the conditions employed in the foregoing tests, a. BFs concentration of approximately 3 weight-percent appears to be the optimum.

ture of 575 F. and held at 575 F. for an additional period of 15 minutes. Thereafter, the bomb and its contents were cooled to room temperature, 3.0 weight-percent of BFa was added, and the bomb was again heated to 575 F., the respective heating and holding periods being 30 and 15 minutes. The bomb was depressurized at reaction temperature, and the contents were gasstripped to a softening point of ZOO-210 F. The product had a color of 16 Gardner and 4 Barrett.

When the above experiment was repeated in a single step (i. e., the Dripolene fraction was polymerized in the presence of BF; and iodine without pretreatment), the product had a color of 14.5 Gardner and 3.5 Barrett.

While I have described the process of my invention in connection with certain specific embodiments thereof, and have illustrated my invention with examples employing certain specific charging stocks and operating conditions, it is to be understood that I am not limited thereto, but may practice my invention in accordance with the broad disclosure thereof. It is further to be understood that any modifications or equivalents that would ordinarily occur to one skilled in the art are to be considered as lying within the scope of my invention.

In accordance with the foregoing description, I claim as my invention:

1. A process for making a resin from a normally liquid mixture of unsaturated hydrocarbons obtained in the pyrolysis of a normally gaseous hydrocarbon having at least two carbon atoms in the molecule, which comprises contacting said normally liquid mixture of unsaturated hydrocarbons with above about 0.5 percent by weight of boron trifluoride and at least about 0.02 percent by weight of iodine at a temperature above about 500 F., whereby a portion of said unsaturated hydrocarbons is converted into a thermoplastic resin of low iodine number and light color, and recovering said resin from the reaction product.

2. A process for making a resin from a normally liquid mixture of unsaturated hydrocarbons obtained in the pyrolysis of a normally gaseous hydrocarbon having at least two carbon atoms in the molecule, which comprises contacting said normally liquid mixture of unsaturated hydrocarbons with between about 0.5 and 5 percent by weight of boron trifluoride and between about 0.02 and 2.0 percent by weight of iodine at a temperature between about 500 and 650 F., whereby a portion of said unsaturated hydrocarbons is converted into a thermoplastic resin of idoine number below about 80 and light color, and recovering said resin from the reaction product.

3. A process for making a resin from a normally liquid mixture of unsaturated hydrocarbons obtained in the pyrolysis of a normally gaseous hydrocarbon having at least two carbon atoms in the molecule, which comprises contacting said normally liquid mixture of unsaturated hydrocarbons with between about 0.5 and 5 percent by weight of boron trifluoride and around 0.05 percent by weight of iodine at a temperature around 575 F., whereby a portion of said unsaturated hydrocrabons is converted into a resin, and removing catalyst and low-boiling components from the reaction product, whereby a thermoplastic resin is obtained having an iodine number below about and a Barrett color lighter than about 4.

4. A process for making a resin from a vnormally liquid mixture of unsaturated hydrocarbons obtained in the pyrolysis of a normally gaseous hydrocarbon having at least two carbon atoms in the molecule, which comprises separating a distillate fraction from said normally liquid mixture of unsaturated hydrocarbons, contacting said distillate fraction with above about 0.5 percent by weight of boron trifluoride and at least about 0.02 percent by weight of iodine at a temperature between about 500 and 650 F., whereby a portion of said unsaturated hydrocarbons is converted into a thermoplastic resin of low iodine number and light color, and recovering said resin from the reaction product.

5. A process for making a resin from 9. normally liquid mixture of unsaturated hydrocarbons obtained in the pyrolysis of a normally gaseous hydrocarbon having at least two carbon atoms in the molecule, which comprises separating a 0-80 volume percent distillate fraction from said normally liquid mixture of unsaturated hydrocarbons, contacting said distillate fraction with between about 0.5 and 5 percent by weight of boron trifluoride and between about 0.02 and 2.0 percent by weight of iodine at a temperature between about 500 and 650 F., whereby a portion of said distillate fraction is converted into a resin, flashing boron trifluoride from the reaction mixture at a temperature between about 500 and 650 F., and stripping the reaction product to a ball-and-ring softening point between about and 250 F., whereby a hydrocarbon resin is obtained having an iodine number below about 80 and a Barrett color lighter than about 4.

FRANCIS T. WADSWOR'I'H.

No references cited. 

1. A PROCESS FOR MAKING A RESIN FROM A NORNMALLY LIQUID MIXTURE OF UNSATURATED HYDROCARBONS OBTAINED IN THE PYROLYSIS OF A NORMALLY GASEOUS HYDROCARBON HAVING AT LEAST TWO CARBON ATOMS IN THE MOLECULE, WHICH COMPRISES CONTACTING SAID NORMALLY LIQUID MIXTURE OF UNSATURATED HYDROCARBONS WITH ABOVE ABOUT 0.5 PERCENT BY WEIGHT OF BORON TRIFLUORIDE AND AT LEAST ABOUT 0.02 PERCENT BY WEIGHT OF IODINE AT A TEMPERATURE ABOVE ABOUT 500* F., WHEREBY A PORTION OF SAID UNSATURATED HYDROCARBONS IS CONVERTED INTO A THERMOPLASTIC RESIN OF LOW IODINE NUMBER AND LIGHT COLOR, AND RECOVERING SAID RESIN FROM THE REACTION PRODUCT. 